CN115763728A - Preparation method of anode material for water system electrolyte - Google Patents
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- CN115763728A CN115763728A CN202211378681.6A CN202211378681A CN115763728A CN 115763728 A CN115763728 A CN 115763728A CN 202211378681 A CN202211378681 A CN 202211378681A CN 115763728 A CN115763728 A CN 115763728A
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Abstract
The invention belongs to the technical field of electrochemical energy storage devices, and particularly relates to a preparation method of a positive electrode material for a water system electrolyte, which comprises the following steps: firstly, adding ammonium dihydrogen phosphate, a reducing agent and a carbon source into an aqueous solution, heating and stirring until a solute is completely dissolved, then adding sodium carbonate, ammonium metavanadate, ferric nitrate and sodium tungstate, continuously heating and stirring until the solute is completely dissolved, then heating in a water bath until the water content is completely evaporated, then carrying out vacuum drying, grinding and tubular furnace sintering to obtain carbon-coated sodium ion fast conductor crystal powder, and finally mixing the carbon-coated sodium ion fast conductor crystal powder with a conductive agent and a binder to form a water system sodium ion battery anode; the anode material prepared by the invention has the characteristics of excellent stability, energy storage performance, cycle performance, low material cost, high safety and the like.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage devices, and particularly relates to a preparation method of a positive electrode material for a water system electrolyte.
Background
Sodium ion batteries have been introduced into battery research systems for a long time, but the development of sodium ion batteries is delayed compared with that of lithium ion batteries due to the excellent performance of lithium ion batteries, but as the lithium ion batteries are developed to a saturation stage, the defects of the development of a large number of lithium ion batteries begin to emerge gradually. The problems of rare lithium ion battery resources, uneven resource distribution, great development difficulty and the like make the energy industry urgently need to search for green battery materials with rich resources.
In recent studies, sodium ion batteries have received much attention, in which sodium and lithium belong to the same main group element, giving a certain similarity in physicochemical properties of substances. Sodium is also considered a promising candidate to complement lithium ion batteries with abundant natural abundance, lower price, and intercalation chemistry similar to that of lithium. However, the explosion events of the organic polymer batteries are rare at present, and the extremely high energy density is a double-edged sword. Much research is currently being conducted to study safer water-based batteries to supplement the vacancy in the field of large-scale energy storage. The sodium super-ion conductor structure material is known as a channel for rapid diffusion of sodium ions, and the typical material of the structure, namely sodium vanadium phosphate, theoretically has high ionic conductivity and high stability. However, the sodium vanadium phosphate can be dissolved seriously during charging and discharging in an aqueous environment, and the application of the material in an aqueous sodium ion battery is greatly limited.
The patent with publication number CN111082162A discloses a water system sodium ion battery, wherein a positive electrode active material is potassium ion doped vanadium sodium phosphate particles coated with a carbon layer and a carbon nitrogen layer, wherein the doped potassium ion can play a role in supporting a crystal structure, and specifically, as the radius of the potassium ion is larger than that of the sodium ion, a small amount of potassium ion is doped in the vanadium sodium phosphate crystal, the stability of the structure can be increased in the process of inserting and removing the sodium ion; the coated carbon layer and the carbon nitrogen layer can play a role in increasing the conductivity of the sodium vanadium phosphate, but the electrolyte applicable to the active material in the scheme consists of sodium hypochlorite, acetonitrile and water, and the acetonitrile and the sodium hypochlorite are substances which are not friendly to the environment and organisms.
The patent publication No. CN107895789A discloses a reduction-oxidation graphene coated sodium vanadium phosphate microsphere nano material, and a preparation method and an application thereof, wherein a graphene layer is used as a coating layer, so that the dissolution of active substances is greatly reduced, and the conductivity of the material is also improved. The method adopts glucose as a carbon source and adds transition metal for doping, so that the cost is reduced, and the stability of the sodium vanadium phosphate is ensured.
The patent with publication number CN114864929A discloses a preparation method of a modified sodium ion battery anode material with a micro-nano structure, and the invention mainly adopts a ball milling method to prepare sodium iron phosphate with a chemical formula of NaFePO 4 Typically olivine crystal structure materials. However, sodium iron phosphate with an olivine structure does not have the property of fast conductivity of sodium ions, the main application field of the sodium iron phosphate is organic traditional batteries, and the weak ion transmission rate makes the sodium iron phosphate unsuitable for water-based battery environments.
The patent with publication number CN109650348A discloses a transition metal chalcogenide nanosheet layer material and a preparation method thereof, a battery cathode material, a secondary battery and an application thereof, the invention adopts transition metal salt to prepare a layered oxide after dissolution, and obtains a lamellar material after vulcanization, but the scheme mainly adopts a coating mode for modification, and the coating modification is difficult to be considered in ion channel and stability.
The patent with publication number CN109755565A discloses a transition metal doped positive electrode material for a sodium ion battery, and preparation and application thereof, and the patent adjusts sodium vanadium fluorophosphate Na by regulating and controlling transition metal 3 V 2 (PO 4 ) 2 F 3 The nature of the/C. However, sodium vanadium fluorophosphate is a good positive electrode material in organic batteries, and the very high redox voltage exceeds the electrolysis voltage of water, so that the sodium vanadium fluorophosphate is difficult to be applied to the field of water-based batteries.
In conclusion, it can be seen that the prevention of the dissolution of the cathode active material in a large amount of free water not only improves the availability of the active material, but also prevents the corrosion of the cathode due to the dissolution effect, and prevents the occurrence of side reactions of the dissolved material on the cathode and the anode.
Disclosure of Invention
The invention provides a preparation method of a positive electrode material for an aqueous electrolyte, aiming at the defects of the prior art.
The method is realized by the following technical scheme:
a preparation method of a positive electrode material for an aqueous electrolyte comprises the following steps:
(1) Adding ammonium dihydrogen phosphate, a reducing agent and a carbon source into water, and heating and stirring until solutes are completely dissolved to obtain a transparent solution;
(2) Adding metal salt into the transparent solution, and continuously heating and stirring until the solute is completely dissolved;
(3) Heating the solution obtained in the step (2) in a water bath and stirring until the water is completely evaporated to dryness;
(4) Vacuum drying the sample with water removed at 120-140 deg.C to obtain loose block sample;
(5) Putting the block sample into a grinding bowl and grinding the block sample into powder;
(6) Placing the powdery sample in a tube furnace, sintering for more than 6 hours at 700-800 ℃ in a protective gas atmosphere to form carbon-coated sodium ion fast conductor crystal powder, and obtaining the anode material Na 3 V 1.5-x Fe 0.5 W x (PO 4 ) 3 ；
(7) And mixing the carbon-coated sodium ion fast conductor crystal powder with a conductive agent and a binder to form the anode of the water system sodium ion battery.
In the step (1), the molar ratio of the ammonium dihydrogen phosphate to the reducing agent to the carbon source is 3: (7-14): (1-3); preferably, the molar ratio of the ammonium dihydrogen phosphate to the reducing agent to the carbon source is 3:7:1.
the carbon source is one or more of citric acid, glucose and polyvinyl alcohol.
The reducing agent is oxalic acid.
The metal salt is sodium carbonate, ammonium metavanadate, ferric nitrate and sodium tungstate.
The molar ratio of ammonium dihydrogen phosphate, sodium carbonate, ammonium metavanadate, ferric nitrate and sodium tungstate in the solution obtained in the step (2) is 30:15:15-X:5: x is more than 0 and less than or equal to 5.
Preferably, the molar ratio of ammonium dihydrogen phosphate, sodium carbonate, ammonium metavanadate, ferric nitrate and sodium tungstate in the obtained solution is 30:15:13:5:2.
the amount of water used was weighed as 15 liters of water per mole of ammonium metavanadate.
The temperature of the water bath heating was 80 ℃.
The protective gas is any one or more of argon, nitrogen, helium and neon.
Preferably, the temperature of the vacuum drying is 120 ℃.
Preferably, the vacuum drying time is 12h.
Preferably, the sintering time is 8h.
The positive electrode material Na 3 V 1.5-x Fe 0.5 W x (PO 4 ) 3 Is iron and tungsten doped vanadium sodium phosphate, wherein the chemical formula of the vanadium sodium phosphate is Na 3 V 2 (PO 4 ) 3 。
In the step (7), the mass ratio of the carbon-coated sodium ion fast conductor crystal powder to the conductive agent to the binder is 8.
In the preparation process, by doping two transition metal elements such as iron and tungsten, the stability of the electrode material in water is greatly improved, so that the electrode material can be applied to the field of water system sodium ion batteries.
Has the advantages that:
(1) The anode material prepared by the invention has high stability, the ferric nitrate and the sodium tungstate are adopted as doping materials, the electrolyte is a sodium sulfate solution, the material cost is low, the safety is high, and the environment is friendly.
(2) The anode material prepared by the invention has excellent energy storage property under the condition of large current of 1A/g.
(3) The anode material prepared by the invention has excellent cycle performance, and the battery capacity retention rate is more than or equal to 90% in 50 cycles.
(4) The anode material prepared by the invention has high specific capacity, and the capacity is about 65 mAh/g.
Drawings
FIG. 1 shows a positive electrode material Na in example 4 3 V 1.5-x Fe 0.5 W x (PO 4 ) 3 The preparation flow chart of (1);
fig. 2 is an XRD pattern of the positive electrode material obtained in example 4;
fig. 3 is a graph of percent cycle capacity for positive electrode materials prepared in examples 1 and 2;
FIG. 4 shows a positive electrode material Na in example 4 3 V 1.5-x Fe 0.5 W x (PO 4 ) 3 A cyclic capacity map of (a);
fig. 5 is a graph of the cycle capacity of the positive electrode materials prepared in examples 1, 2, 3, and 4;
fig. 6 is a graph comparing the color of the initial electrolyte after assembly and the electrolyte after 50 cycles of the positive electrodes prepared in examples 1 to 4.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
A preparation method of a positive electrode material NVP for an aqueous electrolyte comprises the following steps:
(1) According to the proportion that ammonium dihydrogen phosphate, oxalic acid and citric acid are 3:7:1, adding ammonium dihydrogen phosphate, oxalic acid and citric acid into water, and heating and stirring until solutes are completely dissolved to obtain a transparent solution;
(2) According to the weight ratio of ammonium dihydrogen phosphate: sodium carbonate: weighing ammonium metavanadate =6, adding sodium carbonate and ammonium metavanadate into the transparent solution, and continuing heating and stirring until the solute is completely dissolved;
(3) Heating the solution obtained in the step (2) in a water bath at 80 ℃ and stirring until the water is completely evaporated to dryness;
(4) Drying the sample with the water removed in vacuum at 120 ℃ for 12h to obtain a loose massive sample;
(5) Grinding the block sample into powder;
(6) Placing the powdery sample in a tube furnace, and sintering for 6h under the conditions of neon atmosphere and 700 ℃ to form carbon-coated sodium ion fast conductor crystal powder, namely obtaining an anode material NVP;
(7) Mixing the carbon-coated sodium ion fast conductor crystal powder with a conductive agent and a binder according to the mass ratio of 8.
Example 2
A preparation method of a positive electrode material for an aqueous electrolyte comprises the following steps:
(1) According to the proportion that ammonium dihydrogen phosphate, oxalic acid and glucose are 3:7:1, adding ammonium dihydrogen phosphate, oxalic acid and glucose into water, and heating and stirring until solute is completely dissolved to obtain a transparent solution;
(2) According to the weight ratio of ammonium dihydrogen phosphate: sodium carbonate: sodium tungstate: ammonium metavanadate =30:15, X: weighing 20-X molar ratio, adding sodium carbonate, ammonium metavanadate and sodium tungstate into the transparent solution, and continuously heating and stirring until solute is completely dissolved; the specific molar ratio of sodium tungstate to ammonium metavanadate was set to 6 groups, as shown in Table 1 respectively
TABLE 1
| Item | Group of1 | |
|
|
|
|
| Sodium tungstate: ammonium metavanadate | 10:10 | 9:11 | 7:13 | 5:15 | 3:17 | 1:19 |
(3) Heating the solution obtained in the step (2) in a water bath at 80 ℃ and stirring until the water is completely evaporated to dryness;
(4) Drying the sample with the water removed at 140 ℃ for 12h in vacuum to obtain a loose massive sample;
(5) Grinding the block sample into powder;
(6) Placing the powdery sample in a tube furnace, sintering for 6h under the conditions of nitrogen atmosphere and 800 ℃ to form carbon-coated sodium ion fast conductor crystal powder, and obtaining the cathode material NV 1.9 W 0.1 P、NV 1.7 W 0.3 P、NV 1.5 W 0.5 P、NV 1.3 W 0.7 P、NV 1.1 W 0.9 P、NV 1 W 1 P；
(7) Mixing the carbon-coated sodium ion fast conductor crystal powder with a conductive agent and a binder according to the mass ratio of 8.
Example 3
A preparation method of a positive electrode material for an aqueous electrolyte comprises the following steps:
(1) According to the proportion that ammonium dihydrogen phosphate, oxalic acid and glucose are 3:7:1, adding ammonium dihydrogen phosphate, oxalic acid and glucose into water, and heating and stirring until solute is completely dissolved to obtain a transparent solution;
(2) According to the weight ratio of ammonium dihydrogen phosphate: sodium carbonate: ammonium metavanadate: iron nitrate =30:15:15:5, adding sodium nitrate carbonate, ferric salt and ammonium metavanadate into the transparent solution, and continuously heating and stirring until the solute is completely dissolved;
(3) Heating the solution obtained in the step (2) in a water bath at 80 ℃ and stirring until the water is completely evaporated to dryness;
(4) Drying the sample with the water removed at 130 ℃ for 12h in vacuum to obtain a loose massive sample;
(5) Grinding the block sample into powder;
(6) Placing the powdery sample in a tube furnace, sintering for 8h under the condition of argon atmosphere and 750 ℃ to form carbon-coated sodium ion fast conductor crystal powder, and obtaining the cathode material NV 1.5 Fe 0.5 P；
(7) Mixing the carbon-coated sodium ion fast conductor crystal powder with a conductive agent and a binder according to the mass ratio of 8.
Example 4
A positive electrode material for an aqueous electrolyte and a preparation method of a positive electrode comprise the following steps:
(1) According to the proportion that ammonium dihydrogen phosphate, oxalic acid and glucose are 3:7:1, adding ammonium dihydrogen phosphate, oxalic acid and glucose into water, and heating and stirring until solute is completely dissolved to obtain a transparent solution;
(2) According to the weight ratio of ammonium dihydrogen phosphate: sodium carbonate: ammonium metavanadate: iron nitrate: sodium tungstate =30:15:15-X:5: weighing the molar ratio of X, adding sodium carbonate, ferric nitrate, ammonium metavanadate and sodium tungstate into the transparent solution, and continuously heating and stirring until the solute is completely dissolved; the specific molar ratio of ammonium metavanadate, ferric nitrate and sodium tungstate is set as 5 groups, which are respectively shown in table 2:
TABLE 2
(3) Heating the solution obtained in the step (2) in a water bath at 80 ℃ and stirring until the water is completely evaporated to dryness;
(4) Drying the sample with the water removed at 130 ℃ for 12h in vacuum to obtain a loose massive sample;
(5) Grinding the block sample into powder;
(6) Placing the powdery sample in a tube furnace, sintering for 6h under the condition of argon atmosphere and 750 ℃ to form carbon-coated sodium ion fast conductor crystal powder, and obtaining the cathode material NV 1.45 Fe 0.5 W 0.05 P、NV 1.4 Fe 0.5 W 0.1 P、NV 1.3 Fe 0.5 W 0.2 P、NV 1.2 Fe 0.5 W 0.3 P、NV 1.1 Fe 0.5 W 0.4 P；
(7) Mixing the carbon-coated sodium ion fast conductor crystal powder with a conductive agent and a binder according to the mass ratio of 8.
Experimental example 1
The positive electrodes prepared in examples 1 to 4 were used as positive electrodes of sodium ion batteries, and Na was added 1 Ti 2 (PO 4 ) 3 Sodium sulfate is used as an electrolyte to form a sodium ion battery as a negative electrode, and then charge and discharge cycles are carried out under the condition of 1A/g current, wherein the cycle performance is shown in figures 3-5.
FIG. 2 is an X-ray diffraction pattern of the positive electrode material for a sodium-ion battery prepared in example 4; as can be seen from the figure: the doped iron and tungsten has no influence on the crystal structure of the material within fifty percent, and the fast conductor property of the original crystal is kept;
fig. 3 is a graph of percent cycle capacity for the positive electrodes prepared in example 1 and example 2; as can be seen from the figure: the capacity retention of the electrode doped with tungsten is far higher than that of the electrode without any doping;
FIG. 4 is a graph of the cycle capacity of the positive electrode in example 4; as can be seen from the figure: the capacity retention rate of the iron-doped electrode during charging and discharging under the condition of large current is higher and is more than 90%;
fig. 5 is a graph of the cycle capacity of the positive electrodes prepared in example 1, example 2, example 3, and example 4; as can be seen from the figure: the co-doped iron and tungsten electrode has excellent capacity retention.
FIG. 6 is a graph comparing the color of the initial electrolyte after assembly and the electrolyte after 50 cycles for the positive electrodes prepared in examples 1-4; as can be seen from the figure: the positive electrodes prepared in examples 1 to 4 were colorless in color dissolved in the electrolyte in an initial state (no charge and discharge occurred); after 50 cycles, the undoped electrode has serious dissolution phenomenon; the solution changed color from colorless to colored, while the iron-tungsten doped electrode remained colorless after cycling and did not dissolve at all. And both iron-doped and tungsten-doped electrodes inhibit the dissolution of the electrodes to some extent compared to undoped electrodes. It can be known that the transition metal doping screened by the invention can effectively inhibit the dissolution of the sodium vanadium phosphate.
Claims (10)
1. A method for preparing a positive electrode material for an aqueous electrolyte, characterized by comprising the steps of:
(1) Adding ammonium dihydrogen phosphate, a reducing agent and a carbon source into water, and heating and stirring until a solute is completely dissolved to obtain a transparent solution;
(2) Adding metal salt into the transparent solution, and continuously heating and stirring until the solute is completely dissolved;
(3) Heating the solution obtained in the step (2) in a water bath and stirring until the water is completely evaporated to dryness;
(4) Vacuum drying the sample with water removed at 120-140 deg.C to obtain loose block sample;
(5) Putting the block sample into a grinding bowl and grinding the block sample into powder;
(6) Placing the powdery sample in a tube furnace, sintering for more than 6 hours at 700-800 ℃ in a protective gas atmosphere to form carbon-coated sodium ion fast conductor crystal powder, and obtaining the anode material Na 3 V 1.5-x Fe 0.5 W x (PO 4 ) 3 ；
(7) And mixing the carbon-coated sodium ion fast conductor crystal powder with a conductive agent and a binder to form the anode of the water system sodium ion battery.
2. The method according to claim 1, wherein in the step (1), the molar ratio of the ammonium dihydrogen phosphate to the reducing agent to the carbon source is 3: (7-14) and (1-3).
3. The method for preparing a positive electrode material for an aqueous electrolyte according to claim 1, wherein the carbon source is one or more of citric acid, glucose and polyvinyl alcohol; the reducing agent is oxalic acid.
4. The method according to claim 1, wherein in the step (2), the metal salt is sodium carbonate, ammonium metavanadate, ferric nitrate, or sodium tungstate.
5. The method according to claim 1, wherein the molar ratio of ammonium dihydrogen phosphate, sodium carbonate, ammonium metavanadate, iron nitrate and sodium tungstate in the solution obtained in the step (2) is 30:15:15-X:5: x is more than 0 and less than or equal to 5.
6. The method according to claim 1 or 5, wherein the molar ratio of ammonium dihydrogen phosphate, sodium carbonate, ammonium metavanadate, iron nitrate and sodium tungstate in the solution obtained in the step (2) is 30:15:13:5:2.
7. the method for producing a positive electrode material for an aqueous electrolyte according to claim 1, wherein the temperature of the water bath heating is 80 ℃.
8. The method of claim 1, wherein the vacuum drying is performed at 120 ℃ for 12 hours.
9. The method for producing a positive electrode material for an aqueous electrolyte according to claim 1, wherein the sintering time is 8 hours.
10. The method for producing a positive electrode material for an aqueous electrolyte according to claim 1, wherein the positive electrode material is Na 3 V 1.5-x Fe 0.5 W x (PO 4 ) 3 Is iron and tungsten doped vanadium sodium phosphate, wherein the chemical formula of the vanadium sodium phosphate is Na 3 V 2 (PO 4 ) 3 。
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